Film forming compositions and proc



Reissued May 25, 1937 Re,

UNITED STATES PATENT OFFICE FILM FORMING COMPOSITIONS AND PROC- ESS FOR MANUFACTURING SAME Kurt Ripper, Berlin, Germany, assignor, by mesne assignments, to American Cyanamid Company, a corporation of Maine No Drawing. Original application March 20, 1924, Serial No. 700,736. Patent No. 1,734,693, dated November 5, 1929. Divided and application June 22, 1925, Serial No. 38,920. Application for reissue November 4, 1931, Serial No. 573,033. In Austria March 31, 1923 10 Claims. (01. 134-26) This invention relates to the manufacture of such additions have the disadvantage of easily lacquers, films and the like from certain novel cracking in the warmth.

condensation products of urea or its derivatives Example with formaldehyde, and to lacquer compositions thus prepared. 30 parts by weight of pure and neutrally react- 5 The present application is a division of my colng urea are mixed with 100 parts by weight of pending application Serial No. 700,736, filed a 30% aqueous solution of formaldehyde which March 20, 1924, Patent No. 1,687,312, dated not. is free from acid or is neutralized or is slightly 9. 1928, for a process for manufacturing such alkaline, the mixture being heated to boiling in novel water clear urea-formaldehyde condensabDllcr With a reflux condenser. After short 10 tion products. boiling 5 parts by weight of boric acid, dissolved The present invention relates to the f in a little water, are added thereto; the whole ture of non-aqueous lacquers from h novel mixture is thereafter further boiled in the boiler condensation products, namely, the products obwith the reflux condenserf 6 hours After t m by conducmngthe first, stage of the being allowed to stand 1n the cold for several ti between urea and formaldehyde wherein hours, the mass is found to be divided in two the viscous initial products are formed in two layel'slof which the pp One is pcu cdcfi,whcrcessential phases, the first in the absence of free after the tough forming the lower ayer is hydrogen ions and the second in the presence of repeatedly washed with W The gel thus P fr e hydrogen ions, This is accomplished by duced can be dissolved in non-aqueous solvents, adjusting the o in the fi t phase, which is such as for instance epichlorhydrin. Mixed with plated after applying heat'for a short period f softening agents this lacquer solution yields a time to a value f about -1 or below, and by non-cracking coating of lacquer, which is comadjusting the Ch in the second phase to a value P186813 insensitive to any action of waterupwards of 10- but not reaching 10-, and con- I la1m tinuing the reaction is continued by further heat- The process of producmg film'formjng in; The symbol c represents usually grammes lutions which consists in reacting on a urea with of hydrogen ions per liter, a solution of formaldehyde by boiling the mixture The hydrogen ion concentration may also be adiusted to a Ch not exceeding 10 for a short time, thereafter adjusting the hydrogen ion conexpressed by the Symbol pH (chosen by Soren centration of the reaction mixture to a value sen) representing-log H. Therefore the value upwards of a Ch of 104 to cause complete com Ch=m 7 f ff g the valge pHzq' the version of the first formed hydrophile emulsion value Ch: to t 8 pH: colloid in a hydrophobe colloid on further heating. This mode condltctmg the polymerization continuing the reaction by heating the reaction Process in an and medmm results in the forma' mixture cooling the reaction product whereby tion of a hydrophobe emulsion colloid which had the hymphobe colloid is precipitated there been unknown heretofore. If the condensation from separating the precipitated m from Product formed by Short heating of the mixture the water and dissolving it in a non-aqueous solof urea and formaldehyde is heated for prolonged vent time or if the concentration of the hydrogen ions 2. Th process of producing film-forming soluis increased above accrta im t, ydrop tions which consists in reacting on a urea with m l ion coll id is precip y cooline'the a solution of formaldehyde free of acid, initiatreaction mass after accomplishme t o the p ing the reaction by boiling the mixture for a mcrlzatlcn D short time, thereafter adjusting the hydrogen 4 I have fOlmC that the Y D gel thus P ion concentration of the reaction mixture to a duced is far more suitable than any other reacvalue upwards of Ch of 10-1 by addition f acidt o Product Of this d for manufacturing reacting agents to cause complete conversion of q s or fil an h the said hy r ph the first formed hydrophile emulsion colloid in 5 product may be used with non-aqueous solvents hydrophgbe ll id n further heating, nand n-aq us p in a ts t make tinuing the reaction by heating the, reaction mixquers, even when such solvents are not miscible t cooling th ot product whereby the with water. This result is of importance, because hydrophobe colloid is precipitated, separating there are no tempering agents for lacquers 501- the precipitated colloid from the water and disuble in water, and because lacquers made without solving it in a nonaqueous solvent. 5

3. The process of producing film-forming solutions which consists in reacting on a urea with a solution of formaldehyde, the free formic acid content of which solution had been eliminated beiore starting the reaction. initiating the reaction by boiling the mixture for a short time, adlusting the hydrogen ion concentration in the reaction mixture by addition of acid-reacting agents to a value upwards ci-a. Ch of to cause complete conversion of the first formed hydrophile emulsion colloid in a hydrophobe colloid on further heating. continuing the reaction by heating the reaction mixture, cooling the reaction product whereby the hydrophcbe colloid is precipitated therefrom, separating the precipitated colloid from the water, and dissolving it in a nonaqueous solvent.

4. The process of producing film-forming solutions which consists in reacting on a urea with a solution of formaldehyde. the free formic acid content of which solution has been neutralized before starting the reaction-initiating the reaction by boiling the mixture for a short time, adjusting the hydrogen ion concentration of the reaction mixture to a value upwards of a Ch of 10- to cause complete conversion of the iirst formed hydrophile emulsion colloid in a hydrophobe coiloid on'further heating. continuing the reaction by heating the reaction mixture, cooling the reaction product whereby the hydrophobe colloid is precipitated therefrom, separating the precipitated colloid from the water, dissolving it in a nonaqueous solvent and adding a tempering agent.

5. The process of producing film-forming solutions which consists in reacting on a urea with a solution of formaldehyde, the tree formic acid content of which solution had been neutralized before starting the reaction, initiating the reaction by'boiling the mixture for a short time, adiusting the hyr'rogen ion concentration in the reaction mixture to a value upwards of a. Ch of 10- to cause complete conversion of the first formed hydrophile emulsion colloid in a hydrophobe colloid on further heating, continuing the readzion by further heating the reaction mixture, cooling the reaction product whereat the hydrophobe colloid is precipitated therefrom, separating the precipitated colloid from the water, dissolving it in nonaqueous solvents and adding tempering agents, having the property of preventing the films formed by evaporation of the solutions from cracking.

6. A composition comprising a solution of a urea-formaldehyde condensation product in a non-aqueous solvent, said solution containing a tempering agent.

7. A non-aqueous lacquer solution containing a urea-formaldehyde condensation product.

8. A non-aqueous lacquer solution containing a ureasformaldehyde condensation product and a softening agent.

' 9. Acomposition comprising a urea-formaldehyde condensation product and chlorhydrin.

10. A lacquer composition comprising a. hydrophobe reaction product of urea and formaldehyde, soluble and dissolved in a non-aqueous solvent. soluble and dissolved in a non-aqueous organic solvent.

KURT RIPPER CERTIFICATE OF CORRECTION.

Reissue No. 20,383. May 25, 1937.

KURT RIPPER.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line '21, claim 4, for the word "has" read had; and second column, line 31, claim 10, strike out the words and period "soluble and dissolved in a non-aqueous solvent. and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 27th day of July, A. D. 1937.

Henry Van Arsdale (Seal) Acting Commissioner of Patents. 

